CiteULike: dchens Schweizer

Ideal vitrification, barrier hopping, and jamming in fluids of modestly anisotropic hard objects

Galina Yatsenko — 2008-06-10T19:37:48-00:00

Physical Review E (Statistical, Nonlinear, and Soft Matter Physics), Vol. 76, No. 4. (2007)

Our recent theory for the glassy dynamics of fluids and suspensions of hard nonspherical objects is applied to several modestly anisotropic shapes. The role of bond length and aspect ratio is studied for diatomics, triatomics, and spherocylinders. As spherical symmetry is broken the ideal kinetic glass transition volume fraction of all objects increases linearly with aspect ratio with the same slope, in surprising agreement with the jamming phase diagram of hard granular ellipsoids. The ideal glass boundary of all shapes is a nonmonotonic function of aspect ratio which is also in qualitative accord with the jamming behavior of spherocylinders and ellipsoids. The maximum glass volume fraction shifts to higher values, and larger aspect ratios, as the object becomes smoother. Suggestions for why the nonequilibrium jamming and kinetic ideal glass formation (dynamical crossover) boundaries are similar are advanced. Beyond the ideal glass volume fraction the nonequilibrium free energy acquires a localization well and entropic barrier. Although its form is highly nonuniversal, if different shapes are compared at constant barrier height then a good collapse is found. Collapse of the volume fraction dependence of the barrier height for different shapes is also predicted for modest shape anisotropy, but increasingly fails as the aspect ratio exceeds 2. For a given volume fraction the mean barrier hopping times are nonmonotonic functions of aspect ratio. The functional form of this dependence, and order of magnitude variation with aspect ratio, is distinct for each object.

Non-Gaussian effects, space-time decoupling, and mobility bifurcation in glassy hard-sphere fluids and suspensions

Erica Saltzman — 2007-10-29T19:47:05-00:00

Physical Review E (Statistical, Nonlinear, and Soft Matter Physics), Vol. 74, No. 6. (2006)

Brownian trajectory simulation methods are employed to fully establish the non-Gaussian fluctuation effects predicted by our nonlinear Langevin equation theory of single particle activated dynamics in glassy hard-sphere fluids. The consequences of stochastic mobility fluctuations associated with the space-time complexities of the transient localization and barrier hopping processes have been determined. The incoherent dynamic structure factor was computed for a range of wave vectors and becomes of an increasingly non-Gaussian form for volume fractions beyond the (naive) ideal mode coupling theory (MCT) transition. The non-Gaussian parameter (NGP) amplitude increases markedly with volume fraction and is well described by a power law in the maximum restoring force of the nonequilibrium free energy profile. The time scale associated with the NGP peak becomes much smaller than the relaxation time for systems characterized by significant entropic barriers. An alternate non-Gaussian parameter that probes the long time relaxation process displays a different shape, peak intensity, and time scale of its maximum. However, a strong correspondence between the classic and alternate NGP amplitudes is predicted which suggests a deep connection between the early and final stages of cage escape. Strong space-time decoupling emerges at high volume fractions as indicated by a nondiffusive wave vector dependence of the relaxation time and growth of the translation-relaxation decoupling parameter. Displacement distributions exhibit non-Gaussian behavior at intermediate times, evolving into a strongly bimodal form with slow and fast subpopulations at high volume fractions. Qualitative and semiquantitative comparisons of the theoretical results with colloid experiments, ideal MCT, and multiple simulation studies are presented.

Activated Hopping, Barrier Fluctuations, and Heterogeneity in Glassy Suspensions and Liquids

KS Schweizer — 2007-10-29T19:53:08-00:00

J. Phys. Chem. B, Vol. 108, No. 51. (23 December 2004), pp. 19729-19741.

Abstract: Our entropic barrier hopping theory of glassy hard sphere colloidal suspensions is extended to include heterogeneity within a simple trap model framework. The origin of local domains, their size, and the corresponding static barrier fluctuations are attributed to mesoscopic density fluctuations of an amplitude controlled by the bulk compressibility. Based on typical values of the density fluctuation correlation length in dense liquids, the domain size on which correlated hopping occurs is estimated to be 3-4 particle or molecular diameters. Consequences of barrier fluctuations include an increased average relaxation time, faster diffusion, stretched exponential relaxation, diffusion-viscosity decoupling, and a fractional Stokes-Einstein relation. The common origin of the fluctuation effects is the heterogeneity-induced component of the barrier. For colloidal suspensions in the typically studied volume fraction regime the barrier fluctuations have modest consequences, but significantly larger effects are predicted in the putative glassy regime. A statistical dynamical analysis of domain lifetime suggests that for suspensions the relaxation time of mesoscopic collective density fluctuations is at least as long as the single particle hopping time. A general, model-independent analysis of the single molecule incoherent dynamic structure factor for suspensions and thermal liquids has also been performed in the long time and intermediate wavevector regime. The coupling of single particle density and longitudinal stress fluctuations results in a wavevector-dependent apparent diffusion constant and a dynamic correlation length scale which is strongly temperature dependent and directly related to the translation-rotation decoupling factor. This dynamic length is estimated to be 10 times larger than a molecular diameter for tris-naphthyl benzene near the glass transition temperature but shrinks to a molecular size above the crossover temperature that signals the emergence of collective barriers.

Activated hopping and dynamical fluctuation effects in hard sphere suspensions and fluids

Erica Saltzman — 2007-10-29T19:49:58-00:00

The Journal of Chemical Physics, Vol. 125, No. 4. (2006)

Single particle Brownian dynamics simulation methods are employed to establish the full trajectory level predictions of our nonlinear stochastic Langevin equation theory of activated hopping dynamics in glassy hard sphere suspensions and fluids. The consequences of thermal noise driven mobility fluctuations associated with the barrier hopping process are determined for various ensemble-averaged properties and their distributions. The predicted mean square displacements show classic signatures of transient trapping and anomalous diffusion on intermediate time and length scales. A crossover to a stronger volume fraction dependence of the apparent nondiffusive exponent occurs when the entropic barrier is of order the thermal energy. The volume fraction dependences of various mean relaxation times and rates can be fitted by empirical critical power laws with parameters consistent with ideal mode-coupling theory. However, the results of our divergence-free theory are largely a consequence of activated dynamics. The experimentally measurable alpha relaxation time is found to be very similar to the theoretically defined mean reaction time for escape from the barrier-dominated regime. Various measures of decoupling have been studied. For fluid states with small or nonexistent barriers, relaxation times obey a simple log-normal distribution, while for high volume fractions the relaxation time distributions become Poissonian. The product of the self-diffusion constant and mean alpha relaxation time increases roughly as a logarithmic function of the alpha relaxation time. The cage scale incoherent dynamic structure factor exhibits nonexponential decay with a modest degree of stretching. A nearly universal collapse of the different volume fraction results occurs if time is scaled by the mean alpha relaxation time. Hence, time-volume fraction superposition holds quite well, despite the presence of stretching and volume fraction dependent decoupling associated with the stochastic barrier hopping process. The relevance of other origins of dynamic heterogeneity (e.g., mesoscopic domains), and comparison of our results with experiments, simulations, and alternative theories, is discussed. ©2006 American Institute of Physics

Strain softening, yielding, and shear thinning in glassy colloidal suspensions

Vladimir Kobelev — 2008-04-26T00:07:02-00:00

Physical Review E (Statistical, Nonlinear, and Soft Matter Physics), Vol. 71, No. 2. (2005)

A microscopic theory for the dependence on external strain, stress, and shear rate of the transient localization length, elastic modulus, alpha relaxation time, shear viscosity, and other dynamic properties of glassy colloidal suspensions is formulated and numerically applied. The approach is built on entropic barrier hopping as the elementary physical process. The concept of an ideal glass transition plays no role, and dynamical slowing down is a continuous, albeit precipitous, process with increasing colloid volume fraction. The relative roles of mechanically driven motion versus thermally activated barrier hopping and transport have been studied. Various scaling behaviors are found for the relaxation time and shear viscosity in both the controlled stress and shear rate mode of rheological experiments. Apparent power law and/or exponential dependences of the elastic modulus and perturbative and absolute yield stresses on colloid volume fraction are predicted. A nonmonotonic dependence of the absolute yield strain on volume fraction is also found. Qualitative and quantitative comparisons of calculations with experiments on high volume fraction glassy colloidal suspensions show encouraging agreement, and multiple testable predictions are made. The theory is generalizable to treat nonlinear rheological phenomena in other soft glassy complex fluids including depletion gels.

Molecular Theory of Physical Aging in Polymer Glasses

Kang Chen — 2008-03-18T23:12:48-00:00

Physical Review Letters, Vol. 98, No. 16. (2007)

A molecular level theory for the physical aging of polymer glasses is proposed. The nonequilibrium time evolution of the amplitude of long wavelength density fluctuations, and its influence on activated barrier hopping, plays an essential role. The theory predicts temperature-dependent apparent power-law aging of the segmental relaxation time and logarithmic aging of thermodynamiclike properties, in good accord with experiments. A physical origin for the quantitative nonuniversal aspects based on the amplitude of quenched density fluctuations is suggested.

Entropic barriers, activated hopping, and the glass transition in colloidal suspensions

Kenneth Schweizer — 2007-10-29T19:56:08-00:00

The Journal of Chemical Physics, Vol. 119, No. 2. (2003), pp. 1181-1196.

A microscopic kinetic description of single-particle transient localization and activated transport in glassy fluids is developed which combines elements of idealized mode-coupling theory, density functional theory, and activated rate theory. Thermal fluctuations are included via a random force which destroys the idealized glass transition and restores ergodicity through activated barrier hopping. The approach is predictive, containing no adjustable parameters or postulated underlying dynamic or thermodynamic divergences. Detailed application to hard-sphere colloidal suspensions reveals good agreement with experiment for the location of the kinetic glass transition volume fraction, the dynamic incoherent scattering relaxation time, apparent localization length, and length scale of maximum nongaussian behavior. Multiple connections are predicted between thermodynamics, short-time dynamics in the nearly localized state, and long-time relaxation by entropic barrier crossing. A critical comparison of the fluid volume fraction dependence of the hopping time with fit formulas which contain ideal divergences has been performed. Application of the derivative Stickel analysis suggests that the fit functions do not provide an accurate description over a wide range of volume fractions. Generalization to treat the kinetic vitrification of more complex colloidal and nanoparticle suspensions, and thermal glass-forming liquids, is possible. ©2003 American Institute of Physics.

Dynamical fluctuation effects in glassy colloidal suspensions

Kenneth Schweizer — 2008-03-01T22:36:00-00:00

Current Opinion in Colloid & Interface Science, Vol. 12, No. 6. (December 2007), pp. 297-306.

Fundamental understanding of heterogeneous dynamics in concentrated glassy hard sphere fluids and colloidal suspensions, even at the single particle level, requires major theoretical advances. Recent simulations and confocal microscopy experiments suggest strong nongaussian dynamical fluctuation effects and activated transport emerge well before an apparent kinetic glass transition is reached. New theoretical approaches that can predict the observable signatures of intermittent large amplitude motions and the associated fluctuation phenomena are discussed. Comparisons are made with experiments, computer simulations, and prior theory for average dynamical properties.